Thermodynamic formulation of flowing soft matter with transient forces

The Responsive Particle Dynamics model is a very efficient method to account for the transient forces present in complex fluids, such as solutions of entangled polymers. This coarse-grained model considers a solution of particles that are made of a core and a corona. The cores typically interact through conservative interactions, while the coronae transiently penetrate each other to form short-lived temporary interactions, typically of entropic origin. In this study, we reformulate the resulting rheological model within the general framework of nonequilibrium thermodynamics called General Equation for the Nonequilibrium Reversible-Irreversible Coupling. This allows us to determine the consistency of the model, from a mechanistic and thermodynamic point of view, and to isolate the reversible and irreversible contributions to the dynamics of the model system. © 2012 Springer-Verlag Berlin Heidelberg.

Revealing lithium-silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.

Discrete multicomponent model for biodiesel spray combustion simulation

An important first step in spray combustion simulation is an accurate determination of the fuel properties which affects the modelling of spray formation and reaction. In a practical combustion simulation, the implementation of a multicomponent model is important in capturing the relative volatility of different fuel components. A Discrete Multicomponent (DM) model is deemed to be an appropriate candidate to model a composite fuel like biodiesel which consists of four components of fatty acid methyl esters (FAME). In this paper, the DM model is compared with the traditional Continuous Thermodynamics (CTM) model for both diesel and biodiesel. The CTM model is formulated based on mixing rules that incorporate the physical and thermophysical properties of pure components into a single continuous surrogate for the composite fuel. The models are implemented within the open-source CFD code OpenFOAM, and a semi-quantitative comparison is made between the predicted spray-combustion characteristics and optical measurements of a swirl-stabilised flame of diesel and biodiesel. The DM model performs better than the CTM model in predicting a higher magnitude of heat release rate in the top flame brush region of the biodiesel flame compared to that of the diesel flame. Using both the DM and CTM models, the simulation successfully reproduces the droplet size, volume flux, and droplet density profiles of diesel and biodiesel. The DM model predicts a longer spray penetration length for biodiesel compared to that of diesel, as seen in the experimental data. Also, the DM model reproduces a segregated biodiesel fuel vapour field and spray in which the most abundant FAME component has the longest vapour penetration. In the biodiesel flame, the relative abundance of each fuel component is found to dominate over the relative volatility in terms of the vapour species distribution and vice versa in the liquid species distribution. © 2014 Elsevier Ltd. All rights reserved.